CN102015773A - Method of conversion of carbohydrate polymers to value-added chemical products - Google Patents

Method of conversion of carbohydrate polymers to value-added chemical products Download PDF

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CN102015773A
CN102015773A CN2009801152390A CN200980115239A CN102015773A CN 102015773 A CN102015773 A CN 102015773A CN 2009801152390 A CN2009801152390 A CN 2009801152390A CN 200980115239 A CN200980115239 A CN 200980115239A CN 102015773 A CN102015773 A CN 102015773A
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metal halide
ionic liquid
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Z·C·张
Y·苏
H·M·布朗
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Battelle Memorial Institute Inc
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    • C07—ORGANIC CHEMISTRY
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    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
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    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
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    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
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Abstract

Methods are described for conversion of carbohydrate polymers in ionic liquids, including cellulose, that yield value-added chemicals including, e.g., glucose and 5-hydroxylmethylfurfural (HMF) at temperatures below 120 DEG C. Catalyst compositions that include various mixed metal halides are described that are selective for specified products with yields, e.g., of up to about 56% in a single step process.

Description

Carbohydrate polymer changes into the method for added value chemical products
The present invention finishes under government supports according to the DE-AC05-76RLO1830 contract that USDOE is authorized.Government has some right in the present invention.
The field of the invention
Generality of the present invention relates to the conversion of carbohydrate and more particularly, relates to carbohydrate polymer and uses the mixed metal halide catalyzer to obtain the conversion that has the added value chemical products to be carried out in ionic liquid.
Background of the present invention
Mierocrystalline cellulose is the complicated polymer chain that is present in the biomass.For cellulose conversion being become other fuel, need be hydrolyzed to obtain the unibody construction section, obtain required chemical from this unibody construction section.Hydrolysis reaction is subjected to the influence of structure and composition characteristic such as degree of crystallinity and polymer chain length consumingly, and they all have influence on required product yield.At present, depolymerization is the bottleneck of generally acknowledging in the conversion of cellulosic material.Be intended to improve Mierocrystalline cellulose depolymerization method in Aquo System although people have carried out a lot of research work, the progress that obtains is limited, and this part ground is owing to the shortage of Mierocrystalline cellulose solubleness in water.Cellulosic enzymic hydrolysis is that effectively still it is peculiarly slow at ambient temperature, and also is subjected to easily polluting from the pollutent of various biomass components.Mineral acid has been studied catalytic hydrolysis under various acid concentrations and temperature widely, but the degraded of products therefrom remains problem.A kind of this type of product, 5 hydroxymethyl furfural (HMF) also is known as 5-methylol-furfural, is the versatile platform chemical that is used for the production of the chemical of wide region and fuel (they are at present from oil production).Therefore wish and cellulosic material directly can be originated as the glucose of HMF production usefulness.Can not make cellulose hydrolysis become the fact of glucose at low temperatures is that cellulosic direct utilization is provided with sizable obstacle.Therefore, need new method at low temperatures carbohydrate polymer to be changed into the chemical of added value.Advantage of the present invention and novel features will be set forth below, and be clear that from narration and explanation here.These narrations should be regarded of the present invention illustrating as, in no case think restrictive.
General introduction of the present invention
The present invention is the method that the carbohydrate polymer selective conversion becomes to have the chemical of the centre of added value and end-use.This method comprises: carbohydrate polymer is enough to for one section make carbohydrate polymer change into the time of required carbohydrate derivates and product in the ionic liquid and heating that comprises catalyzer under preselected temperature, and this catalyzer comprises at least two kinds of metal halides or the metal-salt of preselected ratio.Carbohydrate polymer for example includes, but not limited to, Mierocrystalline cellulose, hemicellulose, cellobiose, Star Dri 5, starch, or other selected carbohydrate.Reaction process described here use ionic liquid as reaction medium and various mixed metal halide as catalysts.In reaction medium, decrystallization of these mixed metal halide catalysis necessity and hydrolysis reaction are so that change into carbohydrate polymer or parent polysaccharide required and/or the reaction product of added value is arranged.In various embodiments, the mixed metal halide catalyzer comprises CuCl 2With at least a other metal halide, for example, CrCl 2, CrCl 3, PdCl 2, FeCl 3, LaCl 3, NiCl 2, CoCl 2, but be not limited to these.The mixed metal halide catalyzer comprises at least two kinds of metal halides, or metal-salt, wherein first kind of metal halide or metal-salt account for the 50%-1% that the 50%-99% of catalyzer total mole number and second kind of metal halide or metal-salt account for the catalyzer total mole number.In another embodiment, this carbohydrate polymer is a Mierocrystalline cellulose, and this catalyzer is the paired metal halide, for example, and [CuCl 2: CrCl 2] and the carbohydrate product comprise HMF.In another embodiment, this carbohydrate product comprises for example glucose of carbohydrate monomer.In another embodiment, this carbohydrate product comprises HMF.Temperature and reaction times are through selecting, so that farthest obtain selected carbohydrate and at utmost reduce product degradation.The temperature that transforms is preferably in about 100 ℃-Yue 180 ℃ of scopes.More preferably, the temperature of conversion is to be lower than about 120 ℃.The needed time of conversion of realizing carbohydrate polymer is the time in about 0.01 hour-Yue 8 hours scopes preferably, but be not limited thereto.Understanding more fully of the present invention will obtain by following narration with reference to the accompanying drawings, and wherein the same numbers in different accompanying drawings is represented identical structure or unit.
The summary of accompanying drawing
Fig. 1 has shown that carbohydrate polymer changes into the schema of the generalization processing step of added value chemical products in ionic liquid.
Fig. 2 has provided the pairing [CuCl that comprises the composition metal halide of various amounts by use 2: CrCl 2] metal halide catalyst, from the product yield of cellulosic conversion acquisition.
Fig. 3 has provided the pairing [CuCl that comprises the composition metal halide of various amounts by use 2: PdCl 2] metal halide catalyst, from the product yield of cellulosic conversion acquisition.
Fig. 4 has provided by use pairing [CuCl under the catalyst cupport value of selecting 2: CrCl 2] metal halide catalyst, from the product yield of cellulosic conversion acquisition.
Fig. 5 has provided by use pairing [CuCl under the catalyst cupport value of selecting 2: CrCl 2] metal halide catalyst, the product yield that obtains from the conversion of cellobiose and maltose.
Detailed description of the present invention
Described herein is for cellulose and method and the carbon monoxide-olefin polymeric of other carbohydrate polymer in the conversion of ionic liquid. Following term defines so that understand. " ionic liquid " is to have certain fusing point or be the salt of liquid under about 100 ℃ temperature being lower than. The ionic liquid of use related to the present invention comprises 1-R1-3-R 2-imidazoles
Figure BPA00001250922500031
Halide, wherein R1And R2General formula (CxH 2x+1) alkyl, x=1-18 wherein. Exemplary ionic liquid for example includes, but not limited to, the 1-ethyl-3-methylimidazole
Figure BPA00001250922500032
Chloride ([EMIM] Cl); 1-butyl-3-methylimidazole
Figure BPA00001250922500033
Chloride ([BMIM] Cl), the 1-ethyl-3-methylimidazole
Figure BPA00001250922500034
Bromide ([EMIM] Br) and their bond. The nomenclature that is used for the expression ionic liquid is here passed through square brackets for example [EMIM] or [EMIM]+Identify for example 1-ethyl-3-methyl-imidazoles of ionic liquid
Figure BPA00001250922500035
The cationic moiety of salt. The anionicsite of ionic liquid is halogen (for example, Cl or Br for example; Or Cl-Or Br-) be to identify (for example, [EMIM] Cl or [EMIM] by the placement outside square brackets+Cl -). Unless otherwise mentioned, otherwise, have or do not have the name of the ionic liquid of ionic charge to be used interchangeably, for example, [EMIM]+Cl -Or [EMIM] Cl. " imidazoles
Figure BPA00001250922500036
Salt " refer to be selected from the cationic moiety of the ion formation type salt in the heterocyclic aromatic compounds of the imidazole type with following formula [S1]:
Figure BPA00001250922500037
Here, R 1And R 2Be general formula (C xH 2x+1) alkyl, x=1-18 wherein.Following term also defines.
Ionic liquid makes preselected carbohydrate polymer or polysaccharide remove crystallization and makes polymkeric substance or polysaccharide is dissolved in the ionic liquid.Dissolving is that carbohydrate polymer or polysaccharide are dissolved into the chemical process in the ionic liquid.The dissolving of Shi Yonging here is included as provides uniform mixture needed whole suitable solvent temperatures, this mixture comprises: 1) carbohydrate polymer, 2) preselected mixed metal halide (or other selected counter ion) catalyzer, with 3) ionic liquid, still get rid of any depolymerization or the hydrolysis of polymkeric substance." solvent temperature " or swelling temperature refer to the preselected temperature of the required solubleness of the carbohydrate polymer that best realization is selected in the ionic liquid of selecting, and it without limits.
The a series of necessary conversion reaction of mixed metal halide (or other metal-salt) catalyst in ionic liquid of the conversion that is used for carbohydrate polymer described, comprising hydrolysis that for example obtains required carbohydrate converted product and dehydration reaction here.Following term is used to describe mixed metal halide or mixed metal salt catalyst concentration here:
" total catalyst charge capacity " be by following equation [1] provide for the defined amount of conversion catalyst:
Figure BPA00001250922500041
Here, catalyzer 1 is first kind of metal halide or first kind of metal-salt.Catalyzer 2 is second kind of metal halide or other second kind of metal-salt.Here " percentage catalyzer composition " (the % composition) of Shi Yonging each metal halide that is meant in catalyst system to be comprised or the percentage ratio of metal-salt equal 100% when adding together.Comprise CuCl for forming with the percentage catalyzer of [95:5] 2And CrCl 2Catalyst system, the amount of each metal halide component (mmol/g ionic liquid) is obtained by equation [2] and [3]:
Figure BPA00001250922500042
Figure BPA00001250922500043
Hydrolysis is the depolymerization or finally obtain the chemical process of required converted product with the water reaction in the presence of water of carbohydrate polymer or polysaccharide.For example, cellulosic hydrolysis obtains monose (simple sugar) and HMF in ionic liquid, and unexpected low-producing impurity such as levulinic acid are arranged.The conversion of carbohydrate polymer in ionic liquid/mixed metal halide catalyst system here described does not need to use other acid to dewater.In addition, Mierocrystalline cellulose and other complex carbon hydrate in ionic liquid mixed metal halide (or other counter ion) catalyzer catalytic conversion demonstrate highly selective to required chemical products.For example, carbohydrate polymer can change into value-added product selectively according to selected selection of catalysts, and this product includes but not limited to for example glucose, seminose, and/or HMF.Therefore, by the suitable selection of mixed metal halide catalyzer, product and yield can be regulated selectively.Here to be selected catalyzer realizing selected carbohydrate polymer hydrolysis and changing into the relative measurement of the validity on the selected final product term of Shi Yonging " activity ".For example, 50% transformation efficiency of being realized by a kind of mixed metal halide catalyzer has more high reactivity than the catalyzer of realizing 30% transformation efficiency.The low catalyst activity here is defined as and is lower than about 10% product yield.Following term defines with reference to the transformation efficiency of the carbohydrate polymer that further describes below.Here the term of Shi Yonging " selectivity " is to be defined by equation [4]:
Figure BPA00001250922500051
Term " transformation efficiency " is to be defined by equation [5]:
Figure BPA00001250922500052
Here the term of Shi Yonging " yield " is to be defined by equation [6]:
Figure BPA00001250922500053
The compound of furans type is the exemplary types of converted product." furans " is heterocyclic aromatic or the organic compound with general structure [S2] and [S3]:
Figure BPA00001250922500061
Figure BPA00001250922500062
Here, R 1, R 2, R 3And R 4It is the functional group that comprises H for example or C; C may further include O and/or H, has determined for example aldehyde or alcohol functional group." furans " [CAS 110-00-9] (C4H4O) is included in the have structure compound of this type of [S2], wherein R 1And R 2Be H.5 hydroxymethyl furfural (HMF) [CAS No.67-47-O] (chemical formula: C 6H 6O 3), also be known as " hydroxymethylfurfural ", be to have structure chemical derivative [S2], furans, wherein R 1Be alcohol (CH 2OH) group and R 2Be aldehyde (H-C=O) group, here will further describe.Although for example the preferred method that combines with selected catalyst composition is described below cellulosic conversion has been described, but disclosure thing is not limited to the conversion of this exemplary compounds, and is intended to the representative of the conversion of many different carbohydrate polymers and polysaccharide.For example, carbohydrate polymer and the polysaccharide that is suitable for the conversion of the inventive method includes but not limited to for example starch, Mierocrystalline cellulose, hemicellulose and cellobiose.The hard-core meaning.
Cellulose hydrolysis is produced this process need low temperature conversion reaction of glucose, subsequent dewatering production hydroxymethylfurfural (HMF), because glucose and HMF at high temperature degrade.By for example CuCl 2With additional metal chloride CrCl for example 2, PdCl 2, CrCl 3And FeCl 3The pairing metal chloride of forming catalysis effectively is being lower than under 120 ℃ the temperature at 1-ethyl-3-Methylimidazole
Figure BPA00001250922500063
Mierocrystalline cellulose depolymerization in the ionic liquid of muriate (that is [EMIM] Cl).Other imidazoles Halogenide also can be used as ionic liquid.Therefore, illustrate here and the use of the illustrative ionic liquids described does not wish it is to be fit to the ion liquid restriction used.Compare with catalytic those in the control experiment of using mineral acid, when by mixed metal halide catalysis of the present invention the hydrolytic depolymerization speed of Mierocrystalline cellulose in [EMIM] Cl ionic liquid fast at least one order of magnitude.With pairing [CuCl 2: CrCl 2] the catalytic cellulose conversion of mixed metal halide obtains about 56% HMF yield.
Fig. 1 is the embodiment that has shown the method according to this invention, and carbohydrate polymer transforms the method flow diagram of the processing step of usefulness.[beginning].In a step 102, the catalyzer that comprises mixed metal halide or mixed metal salt is by at least two kinds of metal halides of general or mixed metal salt mixes in ionic liquid and then mixture is heated the uniform mixture of acquisition under preselected temperature or solution prepares.The preferred mixing temperature of Preparation of Catalyst is about 150 ℃, but this without limits.Metal halide or the metal-salt total catalyst charge capacity in ionic liquid preferably is selected at about 6mmol/g ionic liquid to the ion liquid scope of about 370mmol/g; More particularly, at about 12mmol/g ionic liquid to the ion liquid scope of about 185mmol/g; The most especially, at about 18mmol/g ionic liquid to the ion liquid scope of about 60mmol/g.In the total catalyst charge capacity, two kinds of metal halides or metal-salt are included in approximately the % catalyzer between [95:5] % peace treaty [50:50] % and form.More particularly, this % catalyzer is formed approximately between extremely about [70:30] % of [99:1] %.In another step 104, carbohydrate polymer is introduced in ionic liquid/catalyst system.Polymkeric substance preferably at room temperature is added in the reaction mixture so that dispose.The concentration that is incorporated into the carbohydrate polymer in the ionic liquid be at about 10wt% to about 30wt% scope, the solubility limit in selected ionic liquid at the most still.Therefore, the hard-core meaning.In another step 106, carbohydrate polymer is under preselected dissolving (swelling) temperature and to be enough to dissolving the dissolution time of (swelling) polymkeric substance in ionic liquid and heating.Preferred solvent temperature is between about 100 ℃ and about 150 ℃.Preferred dissolution time is between about 30 minutes and 60 minutes, but is not limited thereto.In another step 108, water is added in the reaction mixture hydrolysis with the initiated polymerization thing.The preferred concentration of water is between about 2wt% and about 20wt% in ionic liquid, but is not limited thereto.Mixture is heated to preselected temperature of reaction subsequently.Preferred temperature of reaction is between about 80 ℃ and about 120 ℃, but is not limited thereto.In another step 110, carbohydrate polymer heats time enough so that carbohydrate polymer is changed into preselected final product in the presence of catalyzer in containing ion liquid water.The temperature of reaction that transforms preferably is selected between about 80 ℃ to 120 ℃, but without limits.In-Yue 8 hours scopes that the time of reaction typically is chosen in about 0.01 hour, but be not limited thereto.In final step 112, reaction product is separated from ionic liquid by the those of ordinary skill separation known method in the use chemical field and is reclaimed, for example vacuum distilling, organic solvent extraction, and/or from hydrophilic solvent other separation method [end] of separation of organic substances.Those technician of chemical field will recognize that temperature and reaction times will partly depend on required reaction product.Therefore, in scope, should explain by listed temperature of reaction and reaction times without limits.The total overall reaction parameter that those technician expect or use after using for reference disclosure thing in this area is within the scope of the invention.
Fig. 2 is the graphic representation that has shown the yield of the chemical product that obtains from the conversion of biomass [EMIM] C1 ionic liquid of cellulose.Here, use the pairing [CuCl of the composition metal halide that comprises that various % form 2: CrCl 2] metal halide catalyst.Before transforming, Mierocrystalline cellulose dissolves for some time of 1 hour under 100 ℃ dissolving (swelling) temperature in [EMIM] Cl ionic liquid.The cellulosic material that is used for conversion reaction is the about 10wt% (for example, 50mg Mierocrystalline cellulose/500mg ionic liquid) at ionic liquid.Total catalyst charge capacity (CuCl in the pairing metal halide catalyst 2And CrCl 2The total amount) be the 37mmol/g ionic liquid.Reaction (conversion) temperature is 120 ℃.The time of reaction is 1 hour.
Fig. 3 has shown to use [CuCl in the pairing metal halide catalyst 2: PdCl 2] various % form the graphic representation of the yield of the chemical product that obtains from the conversion of Mierocrystalline cellulose [EMIM] Cl ionic liquid.The total catalyst charge capacity is held constant at the 37mmol/g ionic liquid.After the interpolation of catalyzer, allow Mierocrystalline cellulose under 100 ℃, in ionic liquid, dissolve (swelling) 1 hour.Reaction times is following 0.5 hour at 120 ℃.In the figure, when for the pairing [CuCl in catalyzer 2: PdCl 2] when this catalyzer of metal halide comprises [80:20] % composition, obtained to surpass 70% total product yield, wherein glucose is main products.The result further shows, at pairing [CuCl 2: PdCl 2] add in the metal halide catalyst system and be low to moderate 5% PdCl 2(that is, the % catalyzer of [95:5] is formed) will be provided at the acceptable product yield in [EMIM] Cl ionic liquid.CuCl therein 2[CuCl as the low concentration component 2: PdCl 2] pairing metal halide catalyst system [that is, the % catalyzer of [10:90] is formed) in, for main PdCl 2The activation of metal halide component will produce and work as PdCl 2Be the activity of low concentration component similar level when (the % catalyzer of [95:5] is formed), though the CuCl of more high capacity amount 2(that is, 10%) is in order to produce and to work as PdCl 2The active similar activity level that is obtained during as low concentration component (that is, 5%) is needed.
Fig. 4 has shown the [CuCl that uses the fixedly % catalyzer composition with [90:10] 2: PdCl 2] the mixed metal halide catalyzer, the graphic representation of the product yield that obtains from the conversion (hydrolysis) of Mierocrystalline cellulose [EMIM] Cl ionic liquid.Total metal halide charge capacity changes in catalyzer.Mierocrystalline cellulose is dissolved among [EMIM] Cl 1 hour under 100 ℃ dissolving (swelling) temperature.With reaction times of catalyzer be under 120 ℃ temperature 1 hour.Illustrated that in the figure total metal chloride charge capacity is for [CuCl 2: PdCl 2] catalyzer promotes the active influence that Mierocrystalline cellulose transforms in [EMIM] Cl ionic liquid.Be lower than～the total catalyst charge capacity of 12mmol/g ionic liquid (IL), the total product yield is about only 2%.When total metal chloride charge capacity was higher than about 23mmol/g ionic liquid, product yield was brought up to rapidly and is higher than 70%.Under the ion liquid total metal chloride charge capacity of about 34mmol/g, observe maximum product yield.The further raising of catalyst loadings can reduce yield, and estimation may be the result of product degradation, and this can prove by the disappearance of cellobiose product.With [CuCl 2: CrCl 2] pairing metal halide catalyst (fixing [90:10] % catalyzer form) obtains similar result.Here, under the ion liquid total catalyst charge capacity of about 48mmol/g, in 1 hour, reaching the highest product yield under 120 ℃.
Fig. 5 has shown to use to have [the CuCl that [90:10] % catalyzer is formed 2: CrCl 2] the pairing metal halide catalyst, the hydrolysis [EMIM] Cl ionic liquid transforms the graphic representation of the product yield that obtains from cellobiose and maltose.Cellobiose and maltose are the simple glucose dimers that obtains from the hydrolysis of Mierocrystalline cellulose and starch respectively.These dimers connect by following key respectively: β-1,4--glycosidic link (cellobiose) or α-1,4-glycosidic link (maltose).The total catalyst charge capacity is maintained at about the 37mmol/g ionic liquid.Reaction times is under 100 ℃ temperature of reaction 3 hours.Second kind of metal halide be CrCl for example 2Interpolation in catalyst mixture has activated α-1 in starch and cellobiose polymkeric substance respectively, and 4--glycosidic link and β-1, the hydrolytic scission of 4-glycosidic link.Here, the result has shown the cellobiose of difference～48% and～53% and the glucose yield that starch transforms.Using the Mierocrystalline cellulose of mixed metal halide catalyzer and total speed of the conversion of other carbohydrate polymer in ionic liquid is with relevant by the speed of the single reactions steps of catalyst activation (comprising for example decrystallization, depolymerization and hydrolysis) in conversion process.
The following example is used for promoting further understanding of the present invention.
Embodiment 1
(reference examples: do not have catalyzer)
200mg (99%) Mierocrystalline cellulose is blended in 2g (99.5%) [EMIM] the Cl ionic liquid.Add 50 μ L H 2O and mixture are 180 ℃ of heating down.Do not add catalyzer.The highest yield of glucose be in 25 minutes, obtain 24%.Form 5%HMF.Product degradation then reduces the glucose yield in the long reaction times.The glucose yield drops to 5% after 70 minutes.Be heated to 160 ℃ similar reaction mixture and in 160 minutes, obtain the highest yield of 32% glucose, form about 7%HMF.The longer long reaction times can reduce the glucose yield.The glucose yield drops to 12% after 250 minutes.
Embodiment 2
(cellulosic conversion)
(pairing [CuCl 2: CrCl 2] metal halide catalyst)
Mierocrystalline cellulose (the C that mixed metal catalyst carried out is used in present embodiment research 12H 22O 11)-comprise two glucose units cellulosic carbohydrate polymer derivative-conversion.500mg (99.5%) [EMIM] Cl and pairing [CuCl 2: CrCl 2] the metal halide catalyst mixing, and under 150 ℃, heated 0.5 hour and the acquisition uniform mixture.CuCl 2And CrCl 2% catalyzer composition value in different experiments, change, wherein the total catalyst charge capacity is held constant at the 37mmol/g ionic liquid.Add 50mg (99.5%) Mierocrystalline cellulose and under 100 ℃ dissolving (swelling) temperature, dissolved this Mierocrystalline cellulose in 1 hour in ionic liquid and heating.Add 50 μ LH 2O causes hydrolysis.Conversion was carried out under 120 ℃ temperature of reaction 1 hour.In another experiment, temperature of reaction is that 120 ℃ and reaction times are 2 hours.The result is shown in table 1 and the table 2 respectively.
DTemp=dissolves (swelling) temperature; The DTime=dissolution time;
The RTemp=temperature of reaction; The RTime=reaction times.
The product of cellulose conversion includes but not limited to for example glucose; Fructose; Seminose; Formic acid; Levulinic acid; 1,6-dehydration-β, D-glucose; And HMF.In table 1, with 1 hour reaction times, respectively at [83:17], the % catalyzer of [90:10] and [95:5] was formed down with the highest product yield of mixed metal halide catalyzer acquisition.In table 2,,, under forming, the % catalyzer of [90:10] and [95:5] uses the mixed metal halide catalysis the highest product yield of agent acquisition once more respectively at [83:17] with 2 hours reaction times.Under the % of [50:50] catalyzer composition value, also obtain good yield.Generally speaking, product yield improved along with the augmenting response time.
Embodiment 3
(cellulosic conversion)
(pairing [CuCl 2: PdCl 2] metal halide catalyst)
I.e. [the CuCl of another kind of mixed metal halide catalyzer is used in research 2: PdCl 2] cellulose conversion of being carried out.Repeat the program of embodiment 2.CuCl in metal halide catalyst 2And PdCl 2% catalyzer composition value changed, wherein the total loading amount of metal halide is held constant at the 37mmol/g ionic liquid in catalyzer.Add Mierocrystalline cellulose, under 100 ℃ dissolving (swelling) temperature, be dissolved in the ionic liquid 1 hour then.Temperature of reaction is 120 ℃, and the reaction times is 0.5 hour.The results are shown in the table 3.
Figure BPA00001250922500111
DTemp=dissolves (swelling) temperature; The DTime=dissolution time;
The RTemp=temperature of reaction; The RTime=reaction times.
The product of cellulose conversion includes but not limited to for example glucose; Fructose; Seminose; Formic acid; Levulinic acid; 1,6-dehydration-β, D-glucose; And HMF.The result shows, uses [83:17] % catalyst loadings for metal halide in the mixed metal halide catalyzer, and product yield is maximum.Under the charge capacity of [90:10] and [50:50], obtain medium yield respectively.Under the % catalyst loadings of [90:10] and [17:83], obtain minimum yield respectively.
Embodiment 4
(cellulosic conversion)
(comprise CuCl 2Pairing metal halide catalyst with another kind of metal halide)
Use comprises [CuCl 2] and the another kind of mixed metal catalyst of various second kind of metal chloride study cellulosic conversion.Repeat the program of embodiment 2.Metal halide in catalyzer is fixed on [90:10] % catalyzer and forms.The total catalyst charge capacity of metal halide is held constant at the 37mmol/g ionic liquid in catalyzer.Add Mierocrystalline cellulose, under 100 ℃ dissolving (swelling) temperature, be dissolved in the ionic liquid 1 hour then.Temperature of reaction is 100 ℃, and the reaction times is 4 hours.The results are shown in table 4 and the table 5.
Figure BPA00001250922500121
Figure BPA00001250922500122
DTemp=dissolves (swelling) temperature; The DTime=dissolution time;
The RTemp=temperature of reaction; The RTime=reaction times.
The product of cellulose conversion includes but not limited to for example cellobiose; Glucose; Fructose; Seminose; Formic acid; Levulinic acid; 1,6-dehydration-β, D-glucose; And HMF.Result in table 4 and the table shows that various second kind of metal halide are as component and CuCl 2Be added on together in the mixed metal halide catalyzer, it obtains good product yield for cellulosic conversion.Here, PtCl 2As second kind of metal halide component in the mixed metal halide catalyzer, observe the high reactivity of cellulose conversion.Fe, Pd, Cr, the muriate of Ni and Al is observed medium activity as second kind of metal halide in catalyzer.LaCl 3And MnCl 2As second kind of metal halide, observe minimum activity.
Embodiment 5
(cellulosic conversion)
(the pairing metal salt catalyst that another kind of counter ion are arranged)
Different counter ion (SO 4 2-) for mixed metal salt [CuSO in the conversion of carbohydrate polymer 4: CrCl 3] influence and dissolving (swelling) temperature correlation ground of activity of such catalysts studies.Repeat the program of embodiment 2.Use comprises [CuSO 4: CrCl 3] mixed metal catalyst.CuSO in catalyzer 4With CrCl 3% catalyzer composition value be change, simultaneously the total catalyst charge capacity of metal-salt is held constant at the 37mmol/g ionic liquid in catalyzer.Mierocrystalline cellulose dissolved 1 hour down at 120 ℃.Temperature of reaction is 120 ℃, and the reaction times is 1 hour.The results are shown in the table 6.
Figure BPA00001250922500131
DTemp=dissolves (swelling) temperature; The DTime=dissolution time;
The RTemp=temperature of reaction; The RTime=reaction times.
The product of cellulose conversion includes but not limited to for example cellobiose; Glucose; Fructose; Seminose; Formic acid; Levulinic acid; 1,6-dehydration-β, D-glucose; And HMF.Listed product yield amounts to and does not reach 100%, because some polymer products are not characterized by HPLC.The result shows that counter ion demonstrate slight influence to product yield.In table 6, conversion results is directly relevant with concentration of metal in mixed metal catalyst, and wherein second kind of metal component has great effect for conversion.Result of experiment shows under various dissolvings (swelling) temperature, and is general, improves solvent temperature and can increase product yield.The result is owing to better Mierocrystalline cellulose depolymerization in ionic liquid under higher temperature, and therefore cellulosic more effective conversion is arranged.
Embodiment
(cellulosic conversion)
(pairing [CuCl 2: CrCl 3] metal halide catalyst)
Research dissolution time and temperature are for the influence of the conversion of carbohydrate polymer.Repeat the program of embodiment 2.Use [CuCl 2: CrCl 3] the hybrid metal chloride catalyst.CuCl 2With CrCl 3The change of % catalyzer composition value, simultaneously the total catalyst charge capacity of metal-salt is held constant at the 37mmol/g ionic liquid in catalyzer.Mierocrystalline cellulose dissolved 1 hour down at 80 ℃.Temperature of reaction is 120 ℃, and the reaction times is 1 hour.The results are shown in the table 7.
Figure BPA00001250922500141
DTemp=dissolves (swelling) temperature; The DTime=dissolution time;
The RTemp=temperature of reaction; The RTime=reaction times.
The product of cellulose conversion includes but not limited to for example cellobiose; Glucose; Fructose; Seminose; Formic acid; Levulinic acid; 1,6-dehydration-β, D-glucose; And HMF.The result shows that dissolving (swelling) temperature and dissolution time influence the distribution of product yield and product.The result further shows, [CuCl 2: CrCl 3] under various % catalyzer are formed the effective catalyst in cellulosic conversion.
Embodiment 7
(cellulosic conversion)
(various pairing metal halide catalyst)
Solvent temperature that research promotes and temperature of reaction are for the influence of the conversion of carbohydrate polymer.Repeat the program of embodiment 2.Under forming, various % catalyzer use various pairing metal halide catalysts.The charge capacity of metal halide salt is held constant at the 37mmol/g ionic liquid in catalyzer.Use various reaction parameters.The results are shown in the table 8.
Figure BPA00001250922500151
DTemp=dissolves (swelling) temperature; The DTime=dissolution time;
The RTemp=temperature of reaction; The RTime=reaction times.
Because the not existence of characterize polymers residue, the product yield in table 8 amounts to does not have 100%.The result shows, CrCl 2And CrCl 3Component as mixed metal catalyst is selectively for HMF production, wherein CrCl 2Demonstrate bigger selectivity.For example, use [CuCl with [17:83] % catalyzer composition 2: CrCl 2] cellulosic hydrolysis that catalyzer carried out is (1 hurdle) that took place in 8 hours under 100 ℃ dissolving (swelling) temperature.Here, in the product that reclaims, observe 95% selectivity, 56% yield is arranged for HMF HMF.Has [the CuCl that [10:90] % catalyzer is formed by use 2: CrCl 3] catalyzer, (3 hurdle) took place in cellulosic hydrolysis in 0.5 hour under 140 ℃ dissolving (swelling) temperature, have 41% HMF yield.On the contrary, glucose is with comprising for example [CuCl 2: CrCl 3] (2 hurdle) and [CuCl 2: PdCl 2] the pairing metal halide catalyst on (4 hurdle) forms the product of preponderating of acquisition down at the % of [83:17] catalyzer, obtains 40% and 44% glucose yield respectively.Just as described, the selectivity of product of the conversion reaction of carbohydrate polymer and yield partly depend on solvent temperature and time, temperature of reaction, reaction times, selection of catalysts and the mol ratio of metal halide in mixed metal catalyst.Those technician selected whole parameters after using for reference disclosure thing are within the scope of the invention in this area.Wish to be not limited to the discussion of exemplary test.
Embodiment 8
(cellulosic conversion)
(various pairing metal salt catalyst)
Research dissolution time and temperature are for the influence of the conversion of carbohydrate polymer.Repeat the program of embodiment 2.Use various pairing metal salt catalysts.The change of % catalyzer composition value, the total catalyst charge capacity of metal-salt is held constant at the 37mmol/g ionic liquid in catalyzer simultaneously.Mierocrystalline cellulose dissolved 1 hour down at 100 ℃ and 120 ℃; With dissolving under 140 ℃ 0.5 hour.Temperature of reaction is included in reaction times of 1 hour 120 ℃; With in 4 hours reaction times 80 ℃.The results are shown among the table 9-11.
Figure BPA00001250922500161
Figure BPA00001250922500171
DTemp=dissolves (swelling) temperature; The DTime=dissolution time;
The RTemp=temperature of reaction; The RTime=reaction times.
The product of cellulose conversion includes but not limited to for example cellobiose; Glucose; Fructose; Seminose; Formic acid; Levulinic acid; 1,6-dehydration-β, D-glucose; And HMF.The result shows that dissolving (swelling) temperature is for the big influence of being distributed with of product yield and product.The result shows that further the pairing metal halide catalyst is activated in cellulose conversion under various % catalyzer are formed.When as the halid CuCl of major metal 2Amount when being lower (being lower than about 10%), the pairing metal chloride catalyst does not have enough activity for cellulosic conversion under enough yields.
Embodiment 9
(cellulosic conversion)
(catalyzer that various mixed metal halides are arranged)
The research reaction times is for the influence of the conversion of carbohydrate polymer.Repeat the program of embodiment 2.Under forming, various % catalyzer use various pairing metal halide catalysts.The total catalyst charge capacity of metal halide is held constant at the 37mm0l/g ionic liquid in catalyzer.Mierocrystalline cellulose dissolved 0.5 hour down at 140 ℃.Temperature of reaction is 80 ℃, and wherein the reaction times was respectively 2 hours, 1 hour and 0.5 hour.The results are shown among the table 12-14.
Figure BPA00001250922500181
DTemp=dissolves (swelling) temperature; The DTime=dissolution time;
The RTemp=temperature of reaction; The RTime=reaction times.
Once more, cellulosic converted product includes but not limited to for example cellobiose; Glucose; Fructose; Seminose; Formic acid; Levulinic acid; 1,6-dehydration-β, D-glucose; And HMF.The result shows that the % catalyzer in the pairing metal halide catalyst is formed influences product yield.Under low temperature of reaction, product yield does not have significant difference in the different reaction times.For any given mixed metal halide catalyzer, exist specific catalyst to form, the metal halide catalyst that wherein matches is highly active.When as the halid CuCl of major metal 2Amount when being lower (being lower than about 10%), the pairing metal chloride catalyst does not have enough activity for cellulosic conversion under enough yields.
Embodiment 10
(cellulosic conversion)
(pairing [CuCl 2: CrCl 3] and [CuSO 4: CrCl 3] metal salt catalyst)
Solvent temperature that research promotes and temperature of reaction are for the influence of the conversion of carbohydrate polymer.Repeat the program of embodiment 2.Use two kinds of different pairing metal salt catalysts, [CuCl 2: CrCl 3] and [CuSO 4: CrCl 3].[90:10] % catalyzer of use metal-salt in catalyzer is formed.The charge capacity of metal halide salt is held constant at the 37mmol/g ionic liquid in catalyzer.In first experiment, Mierocrystalline cellulose is 140 ℃ of down dissolvings 0.5 hour, experiences the reaction times of 0.5 hour, 1 hour and 1.5 hours subsequently under 100 ℃ temperature of reaction respectively.In another experiment, Mierocrystalline cellulose is 120 ℃ of down dissolvings 0.5 hour, experiences the reaction times of 0.5 hour, 1 hour and 1.5 hours subsequently under 120 ℃ temperature of reaction respectively.In another experiment, Mierocrystalline cellulose is 120 ℃ of down dissolvings 1.0 hours, experiences the reaction times of 0.5 hour, 1 hour and 1.5 hours subsequently under 120 ℃ temperature of reaction respectively.The result lists in respectively in table 15 and 16.
DTemp=dissolves (swelling) temperature; The DTime=dissolution time;
The RTemp=temperature of reaction; The RTime=reaction times.
Cellulosic converted product includes but not limited to for example cellobiose; Glucose; Fructose; Seminose; Formic acid; Levulinic acid; 1,6-dehydration-β, D-glucose; And HMF.The result shows, under the given % catalyzer the metal-salt in catalyzer was formed, product yield depended on processing condition for example dissolving and temperature of reaction and reaction times.
Although illustrated and described the preferred embodiments of the invention here, under the situation that does not break away from wide region of the present invention, can make many changes and improvements.The summary of front neither wishes to define the application's invention (it is determined by claim), in any case also be not intended to limit the scope of the invention.Therefore appended claim wishes to cover whole these type of changes and improvements within the scope of the invention.

Claims (20)

1. the selective conversion method of carbohydrate polymer, this method may further comprise the steps:
Be enough to for one section make carbohydrate polymer to change into the preselected time of preselected carbohydrate product in the ionic liquid and heating that comprises catalyzer under preselected temperature carbohydrate polymer, this catalyzer comprises at least two kinds of metal halides or metal-salt.
2. the process of claim 1 wherein that this ionic liquid comprises having chemical formula (C xH 2x+1) 1-R 1-3-R 2-imidazoles
Figure FPA00001250922400011
Halogenide, wherein R 1And R 2Be alkyl, x=1-18 wherein.
3. the method for claim 2, wherein this ionic liquid is selected from: 1-ethyl-3-Methylimidazole
Figure FPA00001250922400012
Muriate ([EMIM] Cl); 1-butyl-3-Methylimidazole
Figure FPA00001250922400013
Muriate ([BMIM] Cl), 1-ethyl-3-Methylimidazole
Figure FPA00001250922400014
Bromide ([EMIM] Br) and their binding substances.
4. the process of claim 1 wherein that catalyzer comprises the CuCl of the selected % in extremely about [50:50] % scope of about [97:3] % 2With at least a other metal halide or metal-salt.
5. the method for claim 4, wherein at least a other metal halide is selected from: CrCl 2, CrCl 3, PdCl 2, FeCl 3, LaCl 3, NiCl 2, CoCl 2With their binding substances.
6. the method for claim 1 further is included in before the step of heating carbohydrate polymer the step that carbohydrate polymer is dissolved in the ionic liquid.
7. the process of claim 1 wherein that carbohydrate polymer is selected from: Mierocrystalline cellulose, hemicellulose, cellobiose, Star Dri 5, starch and their binding substances.
8. the method for claim 7, wherein carbohydrate has in ionic liquid the concentration of about 30wt% at the most.
9. the process of claim 1 wherein that the carbohydrate product comprises carbohydrate monomer.
10. the method for claim 9, wherein the carbohydrate product comprises glucose.
11. the method for claim 9, wherein the carbohydrate product comprises 5 hydroxymethyl furfural (HMF).
12. the process of claim 1 wherein that carbohydrate polymer is a Mierocrystalline cellulose, this catalyzer comprises [CuCl 2: CrCl 2] metal halide and this carbohydrate product comprise 5 hydroxymethyl furfural (HMF).
13. the process of claim 1 wherein that invert point is chosen in about 100 ℃-Yue 180 ℃ of scopes; Be chosen in about 0.01 hour to about 8 hours with the transformation time of carbohydrate polymer.
14. be used for the catalyst composition in the conversion of ionic liquid carbohydrate polymer, it comprises:
First kind of metal halide of preselected concentration and second kind of metal halide or second kind of metal-salt.
15. the catalyst composition of claim 14, wherein first kind of metal halide and second kind of metal halide are selected from: CuCl 2, CrCl 2, CrCl 3, PdCl 2, FeCl 3, LaCl 3, NiCl 2, CoCl 2With their binding substances.
16. the catalyst composition of claim 14, wherein first kind of metal halide and second kind of metal halide have the % composition to [50:50] % scope approximately at [95:5] % approximately.
17. the catalyst composition of claim 14, wherein first kind of metal halide and second kind of metal halide have the % composition to [80:20] % scope approximately at [99:1] % approximately.
18. the catalyst composition of claim 14, wherein first kind of metal halide and second kind of metal halide have at the total metal halide substrate concentration in ionic liquid of 6mmol/g ionic liquid to about 37mmol/g ionic liquid scope.
19. the catalyst composition of claim 14, wherein first kind of metal halide and second kind of metal halide have at the total metal halide substrate concentration in ionic liquid of 12mmol/g ionic liquid to about 185mmol/g ionic liquid scope.
20. the catalyst composition of claim 14, wherein first kind of metal halide and second kind of metal halide have at the total metal halide substrate concentration in ionic liquid of about 18mmol/g ionic liquid to about 60mmol/g ionic liquid scope.
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